Process of manufacturing asphalts



Patented Feb. 10, 1942 PROCESS OF MANUFACTURING ASPHALTS Robert E. Burkand Charles H. Whitacre, Cleveland, Ohio, assignors to The Standard OilCompany, Cleveland, Ohio, a corporation of Ohio No Drawing. ApplicationJuly 15, 1938, Serial No. 219,405

5 Claims.

In the production of asphalt it is customary to blow petroleum residuumwith air, the temperature being maintained at about BOO-500 F. Very longcontinued treatment on this order is required for the attainment ofproducts having suitably high melting point and low penetration. We havefound that asphalt-making can be greatly accelerated by suitabletreatment with a small amount of a halide acting catalytically, andparticularly advantageously with the presence of a small amount of ahydrohalogen acid.

To the accomplishment of the foregoing and related ends, the invention,then, comprises the features hereinafter fully described, andparticularly pointed out in the claims, the following. descriptionsetting forth in detail certain illustrative embodiments of theinvention, these being indicative however, of but a few of the variousways in which the principle of the invention may be employed.

The raw material, heavy hydrocarbon material containing aliphatichydrocarbons, usually a heavy petroleum oil from which distillablehydrocarbons have been removed, and which in general is designated asresiduum, is in accordance with the invention heated and agitated in thepresence of a small or catalytic amount of 'a halide catalyst as capableof effecting the Friedel-Crafts reaction, or such as a halide ofzirconium, aluminum, tantalum, copper, tin, zinc, antimony, arsenic,iron, titanium, boron, etc., boron fluoride (BFs), or especiallyaluminum chloride (AlCls), being particularly inexpensive and desirable.The temperature may be for instance 225-450 F. And as hydro-halogen acidwe provide a small amount for instance of hydrogen chloride (HCl)hydrogen bromide (HBr) hydrogen fluoride (HF), hydrogen iodide (HI),such that the treatment of the residuum in the presence of the halidecatalyst is carried out in the presence of the hydro-halogen acid insmall or catalytic amount also, in general the number of mols of halogenacid not exceeding the number of mols of the halogen catalyst. While thereason for the action is not entirely clear,

it may be that the halide acts as a polymerizing catalyst and thehydro-halogen as a promoter. The hydro-halogen acid or promoter may beincorporated at the same time as the halide catalyst or it may beincorporated in the residuum before of after introducing the halide, asmay be desired in any instance, so that the two agents are suitablypresent for action together. For instance, the residuum may be agitatedand the catalyst and the promoter as for example 0.10

to 1.0 per cent of AlCls, advantageously 0.25 per cent, and 0.1 .to 1.0per centof HCl, may be supplied, the temperature being maintained in thedesired range, as for instance 225 to 450 F.. Depending upon the precisespecifications of product desired, such treatment may be applied for asufficient time, as controlled by sampling. Usually /2 to 3 hours issufficient. In some cases it is advantageous to apply the catalytictreatment to residuum which is already oxidized or has been subjected toair-blowing. Thus, for instance a residuum may be heated and agitated inexposure to oxygen or be air-blown to partial conversion to desiredspecifications, for example being air-blown for 12 to 24 hours at atemperature of 400 to 550 F. Then, the catalyst and promoter may beintroduced, and without further supplying oxygen, the residuum may besuitably agitated in the presence of the catalyst and promoter. In caseswhere desired, the airblowing may be continued after the introduction ofthe catalyst and promoter. The time of the catalytic treatment ofmaterial which has been first subjected to oxidation action will dependsomewhat upon the specification characteristics of the finished productdesired. In general, it may be 15 to 60- minutes. The divisionalprocesses respectively of air blowing followed by treating with anacid-acting catalyst, and air blowing with a catalyst followed bytreating with aluminum halide are set forth in our co-pendingapplications Ser. No. 112,348, filed Nov. 23, 1936, now Patent No.2,179,208, dated November '7, 1939, and Ser. No. 219,186, filed July 14,1938, now Patent No. 2,200,914, dated May 14, 1940.

Other modes of applying the principle of the invention may be employed,change being made as regards the details described, provided thefeatures stated in any of the following claims, or the equivalent ofsuch, be employed.

We therefore particularly point out and distinctly claim as ourinvention:

1. In a process of making asphalt, heating and agitating residuum inexposure to oxygen, to partial conversion to desired specifications,then without further supplying oxygen incorporating in the residuum asmall amount of zirconium halide and a small amount of a hydro-halogenacid.

2. In a process of making asphalt, heating and agitating residuum inexposure to oxygen, to partial conversion to desired specifications,then without further supplying oxygen incorporating in the residuum asmall amount of aluminum sistency with from 0.10% to 1.0% of a metalhalide catalyst and from 0.10% to 1.0% of a hydro-halogen acid promoterat a temperature of from 225' F. to 450 F. for a time period of from /2to 3 hours.

5. In a process of making asphalt, heating and agitating petroleumresiduum to asphalt consistency in the presence of oxygen, from 0.10% to1.0% of a metal halide catalyst, and from 0.10%

10 to 1.0% of a hydro-halogen acid promoter.

ROBERT E. BURK. CHARLES H. WHITACRE.

